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1. Substituted Thiols in Dynamic Thiol–Thioester Reactions

   https://doi.org/10.1021/acs.macromol.1c00649  

   Bongiardina, Nicholas J. ; Long, Katelyn F. ; Podgórski, Maciej ; Bowman, Christopher N. ( September 2021 , Macromolecules)

   null (Ed.)
2. Tunable Surfaces and Films from Thioester Containing Microparticles

   https://doi.org/10.1021/acsami.2c05113  

   Martinez, Alina M. ; Cox, Lewis M. ; Darabi, Amir ; Bongiardina, Nicholas J. ; Bowman, Christopher N. ( June 2022 , ACS Applied Materials & Interfaces)
3. Internal Catalysis in Dynamic Hydrogels with Associative Thioester Cross-Links

   https://doi.org/10.1021/acsmacrolett.4c00245  

   Zhang, Vivian ; Ou, Carrie ; Kevlishvili, Ilia ; Hemmingsen, Christina M. ; Accardo, Joseph V. ; Kulik, Heather J. ; Kalow, Julia A. ( May 2024 , ACS Macro Letters)

   Thioesters are an essential functional group in biosynthetic pathways, which has motivated their development as reactive handles in probes and peptide assembly. Thioester exchange is typically accelerated by catalysts or elevated pH. Here, we report the use of bifunctional aromatic thioesters as dynamic covalent cross-links in hydrogels, demonstrating that at physiologic pH in aqueous conditions, transthioesterification facilitates stress relaxation on the time scale of hundreds of seconds. We show that intramolecular hydrogen bonding is responsible for accelerated exchange, evident in both molecular kinetics and macromolecular stress relaxation. Drawing from concepts in the vitrimer literature, this system exemplifies how dynamic cross-links that exchange through an associative mechanism enable tunable stress relaxation without altering stiffness. 

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4. Athermal, Chemically Triggered Release of RNA from Thioester Nucleic Acids

   https://doi.org/10.1002/anie.202110741  

   Mavila, Sudheendran ; Culver, Heidi R. ; Anderson, Alex J. ; Prieto, Tania R. ; Bowman, Christopher N. ( November 2021 , Angewandte Chemie International Edition)

   An athermal approach to mRNA enrichment from total RNA using a self‐immolative thioester linked nucleic acids (TENA) is described. Oligo(thymine) (oT) TENA has a six‐atom spacing between bases which allowed TENA to selectively base‐pair with polyadenine RNA. As a result of the neutral backbone of TENA and the hydrophobicity of the octanethiol end group, oT TENA is water insoluble and efficiently pulled down 93±2 % of EGFP mRNA at a concentration of 10 ng μL⁻¹. Self‐immolative degradation of TENA upon ambient temperature exposure to nucleophilic buffer components (Tris, DTT) allowed recovery of 55±27 ng of mRNA from 3.1 μg of total RNA, which was not statistically different from the amount recovered using Dynabeads® mRNA DIRECT Kit (89±24 ng). Gene expression as measured by RT‐qPCR was comparable for both enrichment methods, suggesting that the mild conditions required for enrichment of mRNA using oT TENA are compatible with RT‐qPCR and other downstream molecular biology applications.

    

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5. Athermal, Chemically Triggered Release of RNA from Thioester Nucleic Acids

   https://doi.org/10.1002/ange.202110741  

   Mavila, Sudheendran ; Culver, Heidi R. ; Anderson, Alex J. ; Prieto, Tania R. ; Bowman, Christopher N. ( November 2021 , Angewandte Chemie)

   An athermal approach to mRNA enrichment from total RNA using a self‐immolative thioester linked nucleic acids (TENA) is described. Oligo(thymine) (oT) TENA has a six‐atom spacing between bases which allowed TENA to selectively base‐pair with polyadenine RNA. As a result of the neutral backbone of TENA and the hydrophobicity of the octanethiol end group, oT TENA is water insoluble and efficiently pulled down 93±2 % of EGFP mRNA at a concentration of 10 ng μL⁻¹. Self‐immolative degradation of TENA upon ambient temperature exposure to nucleophilic buffer components (Tris, DTT) allowed recovery of 55±27 ng of mRNA from 3.1 μg of total RNA, which was not statistically different from the amount recovered using Dynabeads® mRNA DIRECT Kit (89±24 ng). Gene expression as measured by RT‐qPCR was comparable for both enrichment methods, suggesting that the mild conditions required for enrichment of mRNA using oT TENA are compatible with RT‐qPCR and other downstream molecular biology applications.

    

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